Crystal structure across the β to α phase transition in thermoelectric Cu2–xSe

Eikeland, Espen; Blichfeld, Anders B.; Borup, Kasper A.; Zhao, Kunpeng; Overgaard, Jacob; Shi, Xun; Chen, Lidong; Iversen, Bo B.

doi:10.1107/S2052252517005553

Title: Crystal structure across the β to α phase transition in thermoelectric Cu_2–xSe

Journal Article · 12 June 2017 · IUCrJ

DOI: https://doi.org/10.1107/S2052252517005553 · OSTI ID:1373682

^[1];

^[1]; Borup, Kasper A. ^[2]; Zhao, Kunpeng ^[3];

^[1]; Shi, Xun ^[3]; Chen, Lidong ^[3]; Iversen, Bo B. ^[1]

Aarhus Univ., Aarhus (Denmark)
Aarhus Univ., Aarhus (Denmark); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Chinese Academy of Sciences, Shanghai (People's Republic of China)

Here, the crystal structure uniquely imparts the specific properties of a material, and thus provides the starting point for any quantitative understanding of thermoelectric properties. Cu_2–xSe is an intensely studied high performing, non-toxic and cheap thermoelectric material, and here for the first time, the average structure of β-Cu_2–xSe is reported based on analysis of multi-temperature single-crystal X-ray diffraction data. It consists of Se–Cu layers with additional copper between every alternate layer. The structural changes during the peculiar zT enhancing phase transition mainly consist of changes in the inter-layer distance coupled with subtle Cu migration. Just prior to the transition the structure exhibits strong negative thermal expansion due to the reordering of Cu atoms, when approached from low temperatures. The phase transition is fully reversible and group–subgroup symmetry relations are derived that relate the low-temperature β-phase to the high-temperature α-phase. Weak superstructure reflections are observed and a possible Cu ordering is proposed. The structural rearrangement may have a significant impact on the band structure and the Cu rearrangement may also be linked to an entropy increase. Both factors potentially contribute to the extraordinary zT enhancement across the phase transition.

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Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: Danish National Research Foundation; USDOE

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1373682

Report Number(s):: NREL/JA--5J00-68972

Journal Information:: IUCrJ, Journal Name: IUCrJ Journal Issue: 4 Vol. 4; ISSN 2052-2525; ISSN IUCRAJ

Publisher:: International Union of CrystallographyCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Multiformity and fluctuation of Cu ordering in Cu ₂ Se thermoelectric materials Lu, Ping; Liu, Huili; Yuan, Xun Journal of Materials Chemistry A, Vol. 3, Issue 13 https://doi.org/10.1039/C4TA07100J	journal	January 2015
Ionic conductivity and coulometric titration of copper selenide Takahashi, T.; Yamamoto, O.; Matsuyama, F. Journal of Solid State Chemistry, Vol. 16, Issue 1-2 https://doi.org/10.1016/0022-4596(76)90004-9	journal	January 1976
Chemical Stability of (Ag,Cu)2Se: a Historical Overview Brown, David R.; Day, Tristan; Caillat, Thierry Journal of Electronic Materials, Vol. 42, Issue 7 https://doi.org/10.1007/s11664-013-2506-2	journal	March 2013
Colossal Seebeck coefficient in strongly correlated semiconductor FeSb ₂ Bentien, A.; Johnsen, S.; Madsen, G. K. H. Europhysics Letters (EPL), Vol. 80, Issue 1 https://doi.org/10.1209/0295-5075/80/17008	journal	September 2007
The Seebeck coefficient of superionic conductors Mahan, G. D. Journal of Applied Physics, Vol. 117, Issue 4 https://doi.org/10.1063/1.4906617	journal	January 2015
Low-temperature structural and transport anomalies in Cu 2 Se Chi, Hang; Kim, Hyoungchul; Thomas, John C. Physical Review B, Vol. 89, Issue 19 https://doi.org/10.1103/PhysRevB.89.195209	journal	May 2014
Electronic and Ionic Conduction in (Ag _x Cu _{1- x} ) ₂ Se Miyatani, Shin-ya Journal of the Physical Society of Japan, Vol. 34, Issue 2 https://doi.org/10.1143/JPSJ.34.423	journal	February 1973
Enhancement of Thermoelectric Efficiency in PbTe by Distortion of the Electronic Density of States Heremans, J. P.; Jovovic, V.; Toberer, E. S. Science, Vol. 321, Issue 5888, p. 554-557 https://doi.org/10.1126/science.1159725	journal	July 2008
Entropically Stabilized Local Dipole Formation in Lead Chalcogenides Bozin, E. S.; Malliakas, C. D.; Souvatzis, P. Science, Vol. 330, Issue 6011 https://doi.org/10.1126/science.1192759	journal	December 2010
Large Seebeck effect by charge-mobility engineering Sun, Peijie; Wei, Beipei; Zhang, Jiahao Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8475	journal	June 2015
Superior intrinsic thermoelectric performance with zT of 1.8 in single-crystal and melt-quenched highly dense Cu2-xSe bulks Zhao, Lan-ling; Wang, Xiao-lin; Wang, Ji-yang Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep07671	journal	January 2015
Localised Ag+ vibrations at the origin of ultralow thermal conductivity in layered thermoelectric AgCrSe2 Damay, F.; Petit, S.; Rols, S. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep23415	journal	March 2016
Vacancy-Ordered Superstructures in Cu2Se Frangis, N.; Manolikas, C.; Amelinckx, S. Physica Status Solidi (a), Vol. 126, Issue 1 https://doi.org/10.1002/pssa.2211260102	journal	July 1991
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Anharmonic thermal motion of Ag in AgCrSe2: A high-temperature single-crystal X-ray diffraction study Van Der Lee, A.; Wiegers, G. A. Journal of Solid State Chemistry, Vol. 82, Issue 2 https://doi.org/10.1016/0022-4596(89)90285-5	journal	October 1989
High-performance thermoelectric Cu2Se nanoplates through nanostructure engineering Yang, Lei; Chen, Zhi-Gang; Han, Guang Nano Energy, Vol. 16 https://doi.org/10.1016/j.nanoen.2015.07.012	journal	September 2015
Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems Bell, L. E. Science, Vol. 321, Issue 5895, p. 1457-1461 https://doi.org/10.1126/science.1158899	journal	September 2008
Total pattern fitting for the combined size–strain–stress–texture determination in thin film diffraction Lutterotti, Luca Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 268, Issue 3-4 https://doi.org/10.1016/j.nimb.2009.09.053	journal	February 2010
Copper ion liquid-like thermoelectrics Liu, Huili; Shi, Xun; Xu, Fangfang Nature Materials, Vol. 11, Issue 5, p. 422-425 https://doi.org/10.1038/nmat3273	journal	March 2012
Thermoelectric properties of Ag-doped Cu2Se and Cu2Te Ballikaya, Sedat; Chi, Hang; Salvador, James R. Journal of Materials Chemistry A, Vol. 1, Issue 40 https://doi.org/10.1039/c3ta12508d	journal	January 2013
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Structural disorder, anisotropic micro-strain and cation vacancies in thermo-electric lead chalcogenides Christensen, Sebastian; Bindzus, Niels; Sist, Mattia Physical Chemistry Chemical Physics, Vol. 18, Issue 23 https://doi.org/10.1039/C6CP01730D	journal	January 2016
Thermoelectric properties of copper selenide with ordered selenium layer and disordered copper layer Yu, Bo; Liu, Weishu; Chen, Shuo Nano Energy, Vol. 1, Issue 3 https://doi.org/10.1016/j.nanoen.2012.02.010	journal	May 2012
Colossal negative thermal expansion in BiNiO3 induced by intermetallic charge transfer Azuma, Masaki; Chen, Wei-tin; Seki, Hayato Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1361	journal	June 2011
X-ray study of the cation distribution in Cu2Se, Cu1.8Se and Cu1.8S; analysis by the maximum entropy method☆ Yamamoto, K.; Kashida, S. Solid State Ionics, Vol. 48, Issue 3-4 https://doi.org/10.1016/0167-2738(91)90038-D	journal	November 1991
The (hkl) Dependence of Diffraction-Line Broadening Caused by Strain and Size for all Laue Groups in Rietveld Refinement Popa, N. C. Journal of Applied Crystallography, Vol. 31, Issue 2 https://doi.org/10.1107/S0021889897009795	journal	April 1998
Experimental and theoretical investigations of strongly correlated FeSb 2 − x Sn x Bentien, A.; Madsen, G. K. H.; Johnsen, S. Physical Review B, Vol. 74, Issue 20 https://doi.org/10.1103/PhysRevB.74.205105	journal	November 2006
Neutron scattering study of ionic diffusion in Cu–Se superionic compounds Danilkin, S. A.; Avdeev, M.; Sale, M. Solid State Ionics, Vol. 225 https://doi.org/10.1016/j.ssi.2012.02.046	journal	October 2012
Phase transition enhanced thermoelectric figure-of-merit in copper chalcogenides Brown, David R.; Day, Tristan; Borup, Kasper A. APL Materials, Vol. 1, Issue 5 https://doi.org/10.1063/1.4827595	journal	November 2013
Dilatometric study of nonstoichiometric copper selenide Cu2−xSe Vucic, Z.; Horvatic, V.; Milat, O. Solid State Ionics, Vol. 13, Issue 2 https://doi.org/10.1016/0167-2738(84)90046-8	journal	May 1984
Ultrahigh Thermoelectric Performance by Electron and Phonon Critical Scattering in Cu ₂ Se _1-x I _x Liu, Huili; Yuan, Xun; Lu, Ping Advanced Materials, Vol. 25, Issue 45 https://doi.org/10.1002/adma.201302660	journal	September 2013
dc ionic conductivity measurements on the mixed conductor Cu2−xSe Horvatic, M.; Vucic, Z. Solid State Ionics, Vol. 13, Issue 2 https://doi.org/10.1016/0167-2738(84)90045-6	journal	May 1984
Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties Snyder, G. Jeffrey; Christensen, Mogens; Nishibori, Eiji Nature Materials, Vol. 3, Issue 7 https://doi.org/10.1038/nmat1154	journal	June 2004
High thermoelectric figure of merit in heavy hole dominated PbTe Pei, Yanzhong; LaLonde, Aaron; Iwanaga, Shiho Energy & Environmental Science, Vol. 4, Issue 6 https://doi.org/10.1039/c0ee00456a	journal	January 2011
Interstitial Zn Atoms Do the Trick in Thermoelectric Zinc Antimonide, Zn4Sb3: A Combined Maximum Entropy Method X-ray Electron Density and Ab Initio Electronic Structure Study Cargnoni, Fausto; Nishibori, Eiji; Rabiller, Philippe Chemistry - A European Journal, Vol. 10, Issue 16 https://doi.org/10.1002/chem.200400327	journal	August 2004
Relating phase transition heat capacity to thermal conductivity and effusivity in Cu ₂ Se Brown, David R.; Heijl, Richard; Borup, Kasper A. physica status solidi (RRL) - Rapid Research Letters, Vol. 10, Issue 8 https://doi.org/10.1002/pssr.201600160	journal	July 2016
Apparent critical phenomena in the superionic phase transition of Cu _{2- x} Se Kang, Stephen Dongmin; Danilkin, Sergey A.; Aydemir, Umut New Journal of Physics, Vol. 18, Issue 1 https://doi.org/10.1088/1367-2630/18/1/013024	journal	January 2016
New Layered Structures of Cuprous Chalcogenides as Thin Film Solar Cell Materials: Cu 2 Te and Cu 2 Se Nguyen, Manh Cuong; Choi, Jin-Ho; Zhao, Xin Physical Review Letters, Vol. 111, Issue 16 https://doi.org/10.1103/PhysRevLett.111.165502	journal	October 2013
Superstructural ordering in low-temperature phase of superionic Cu2Se Milat, O.; Vucic, Z.; Ruscic, B. Solid State Ionics, Vol. 23, Issue 1-2 https://doi.org/10.1016/0167-2738(87)90079-8	journal	March 1987
Composition-induced phase-transition splitting in cuprous selenide Vučić, Z.; Milat, O.; Horvatić, V. Physical Review B, Vol. 24, Issue 9 https://doi.org/10.1103/PhysRevB.24.5398	journal	November 1981
Preparation and thermoelectric properties of semiconducting Zn4Sb3 Caillat, T.; Fleurial, J. -P.; Borshchevsky, A. Journal of Physics and Chemistry of Solids, Vol. 58, Issue 7 https://doi.org/10.1016/S0022-3697(96)00228-4	journal	July 1997
Influence of the cation disordering on the electronic conductivity of superionic copper selenide Vucic, Z.; Horvatic, V.; Ogorelec, Z. Journal of Physics C: Solid State Physics, Vol. 15, Issue 16 https://doi.org/10.1088/0022-3719/15/16/013	journal	June 1982
Thermoelectric materials: Energy conversion between heat and electricity Zhang, Xiao; Zhao, Li-Dong Journal of Materiomics, Vol. 1, Issue 2 https://doi.org/10.1016/j.jmat.2015.01.001	journal	June 2015
Thinking Like a Chemist: Intuition in Thermoelectric Materials Zeier, Wolfgang G.; Zevalkink, Alex; Gibbs, Zachary M. Angewandte Chemie International Edition, Vol. 55, Issue 24 https://doi.org/10.1002/anie.201508381	journal	April 2016
X-ray diffraction and electron microscopy studies of the room-temperature structure of Cu ₂ Se Kashida, S.; Akai, J. Journal of Physics C: Solid State Physics, Vol. 21, Issue 31 https://doi.org/10.1088/0022-3719/21/31/004	journal	November 1988
Crystal structure of Cu2Se Gulay, Lubomir; Daszkiewicz, Marek; Strok, Oksana Chemistry of Metals and Alloys, Vol. 4, Issue 3/4 https://doi.org/10.30970/cma4.0184	journal	January 2011
Complex thermoelectric materials Snyder, G. Jeffrey; Toberer, Eric S. Nature Materials, Vol. 7, Issue 2, p. 105-114 https://doi.org/10.1038/nmat2090	journal	February 2008
High-performance bulk thermoelectrics with all-scale hierarchical architectures Biswas, Kanishka; He, Jiaqing; Blum, Ivan D. Nature, Vol. 489, Issue 7416, p. 414-418 https://doi.org/10.1038/nature11439	journal	September 2012
Order–Disorder Transition in AgCrSe ₂ : a New Route to Efficient Thermoelectrics Gascoin, Franck; Maignan, Antoine Chemistry of Materials, Vol. 23, Issue 10 https://doi.org/10.1021/cm200581k	journal	May 2011
When thermoelectrics reached the nanoscale Heremans, Joseph P.; Dresselhaus, Mildred S.; Bell, Lon E. Nature Nanotechnology, Vol. 8, Issue 7 https://doi.org/10.1038/nnano.2013.129	journal	June 2013
Low-Temperature Structure and Dynamics in Cu ₂ Se Sirusi, Ali A.; Ballikaya, Sedat; Uher, Ctirad The Journal of Physical Chemistry C, Vol. 119, Issue 35 https://doi.org/10.1021/acs.jpcc.5b06079	journal	August 2015
Huge Thermoelectric Power Factor: FeSb ₂ versus FeAs ₂ and RuSb ₂ Sun, Peijie; Oeschler, Niels; Johnsen, Simon Applied Physics Express, Vol. 2, Issue 9 https://doi.org/10.1143/APEX.2.091102	journal	September 2009
Structure-transformation-induced abnormal thermoelectric properties in semiconductor copper selenide Liu, Huili; Shi, Xun; Kirkham, Melanie Materials Letters, Vol. 93 https://doi.org/10.1016/j.matlet.2012.11.058	journal	February 2013

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CCDC 1543676: Experimental Crystal Structure Determination: JAYHUP : Non-CSD Structure Eikeland, E.; Blichfeld, A. B.; Borup, K. A. https://doi.org/10.5517/ccdc.csd.cc1ntb0t The current record is supplemented by this dataset	dataset	April 2017
CCDC 1543675: Experimental Crystal Structure Determination: JAYHOJ : Non-CSD Structure Eikeland, E.; Blichfeld, A. B.; Borup, K. A. https://doi.org/10.5517/ccdc.csd.cc1nt9zr The current record is supplemented by this dataset	dataset	April 2017
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CCDC 1543673: Experimental Crystal Structure Determination: JAYHEZ : Non-CSD Structure Eikeland, E.; Blichfeld, A.; Borup, K. https://doi.org/10.5517/ccdc.csd.cc1nt9xp The current record is supplemented by this dataset	dataset	April 2017
CCDC 1543669: Experimental Crystal Structure Determination: JAYGIC : Non-CSD Structure Eikeland, E.; Blichfeld, A. B.; Borup, K. A. https://doi.org/10.5517/ccdc.csd.cc1nt9sk The current record is supplemented by this dataset	dataset	April 2017
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Title: Crystal structure across the β to α phase transition in thermoelectric Cu2–xSe

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